The present invention relates to star polymers obtainable by polymerization of vinylaromatic monomers with a branching monomer unit containing at least two vinylaromatic functional radicals in the presence of a catalyst obtainable from A) a transition-metal complex from sub-group II to VIII, B) a cation-forming agent and C), if desired, an aluminum compound.
The present invention furthermore relates to a process for the preparation of these star polymers and to their use for the production of fibers, films and moldings, in particular injection molding materials [sic], and the resultant fibers, films and moldings.
Owing to its crystallinity, syndiotactic polystyrene has a very high melting point of about 270xc2x0 C., high rigidity, tensile strength and dimensional stability, a low dielectric constant and high chemicals resistance. The mechanical property profile is retained even at above the glass transition temperature. The preparation of syndiotactic polystyrene in the presence of metallocene catalyst systems is disclosed, for example, in EP-A-210 615.
The low toughness and poor solubility, even in chlorinated solvents, and the low compatibility in blends with thermoplastics, for example PS, PB, PMMA, PE, PP, EP, PA6, PA66, PET, PBT, ABS, ASA etc., are disadvantageous. Furthermore, crystallization of the syndiotactic polystyrene frequently occurs from a conversion of as low as around 10%.
EP-A-572 990 describes metallocene-catalyzed copolymers of styrene and ethylene which have improved compatibility and high elasticity. However, these copolymers do not have the high stereotacticity and therefore do not achieve the high-temperature properties of syndiotactic polystyrene.
Copolymers of styrene and divinylbenzene are described in EP-A-311 099 and EP-A-490 269. Under the reaction conditions, only one vinyl group of the divinylbenzene reacts. The remaining vinyl groups are used for grafting reactions or crosslinked by means of free radicals on conditioning at about 230xc2x0 C., molecular weights of from 1,000,000 to 6,000,000 only being obtained after this crosslinking reaction.
Star polymers belong to the class of the branched polymers (Falbe, Rxc3x6mpp Chemie Lexikon, Georg Thieme Verlag, 9th Edition, Stuttgart 1992, page 4304). They are usually prepared by polymerization of monomers with polyfunctional initiators, polyaddition of, for example, epoxides onto polyhydric alcohols or coupling of pre-prepared polymers, for example Li polystyrene, onto a center, for example silicon tetrachloride.
It is an object of the present invention to provide star polymers made from vinylaromatic monomers, which polymers simultaneously have high molecular weight and low melt viscosities, and a high end-group functionality for graft reactions, crosslinking reactions and other polymer-analogous reactions. Furthermore, the star polymers should have an essentially syndiotactic structure, ie. have a syndiotacticity of greater than 30%, in particular greater than 60%.
We have found that this object is achieved by the star polymers defined at the outset containing the branching monomer units containing at least two vinylaromatic functional radicals.
These polymers have high molecular weights of from 500,000 to 10,000,000 at the same time as low melt viscosities of less than 500 ml/10 min at 290xc2x0 C. and a weight of 10 kg, and have significantly greater end-group functionalities compared with syndiotactic styrene of comparable molecular weight. In general, the end-group functionality is greater than 0.5 mol %, particularly preferably greater than 0.8 mol %.
These properties can be modified within a broad range by means of the molar ratio between the vinylaromatic monomer and branching monomer units according to the invention. The molar ratio between vinylaromatic monomers and the branching monomer unit is generally from 10,000,000:1 to 10:1.
The novel star polymers have a syndiotacticity greater than 60%, in general greater than 90%.
The branching monomers can, according to the invention, be compounds of the formula I 
where
Ra is hydrogen, halogen or an inert organic radical having up to 20 carbon atoms, where, in a case where pxe2x89xa72, the two radicals Ra may be identical or different and can, together with the metal atom to which they are bonded, form a 3- to 8-membered ring, and Ra may furthermore be a conventional complex ligand if M is a transition metal;
Rb is hydrogen, C1-C4-alkyl or phenyl;
Rc is hydrogen, C1-C4-alkyl, phenyl, chlorine or an unsaturated hydrocarbon radical having 2 to 6 carbon atoms;
M is C, Si, Ge, Sn, B, Al, Ga, N, P, Sb, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn or Cd;
n is 2-6;
m is 0-20; and
p is 0-4;
with the proviso that the sum n+p corresponds to the valence of M.
These monomers can be obtained, for example, via the Grignard compounds of chloro(alkyl)styrenes with the corresponding carbon, metal or transition-metal compounds, for example the halogen compounds. Such reactions have been described, for example, for the case where M is silicon, germanium or tin in K. Nakanishi, J. Chem. Soc. Perkin Trans. I, 1990, page 3362.
Particular preference is given to branching monomer units of the formula I in which M is carbon, silicon, germanium, tin or titanium, since they are readily accessible. The index m is preferably from 0 to 8, particularly preferably from 0 to 4.
The present invention also relates to the novel titanium-containing monomers of the formula Ia 
and in particular the titanium compound of the formula Ib 
where Ra, Rb, Rc, m, n and p are as defined above.
The inert organic radicals Ra are of no great significance for the process. Rather, they serve merely to saturate the free valences on M and can be selected in accordance with ready availability. For example, aliphatic, cycloaliphatic, aryl, heteroaryl or aralkyl radicals are suitable. Examples of aliphatic radicals are alkyl, alkoxy, alkenyl and alkynyl radicals having, for example, from 1 to 2 or 20 carbon atoms. Examples of cycloaliphatic radicals are cycloalkyl radicals having 3 to 8 carbon atoms. A methylene group in the alkyl or cycloalkyl radicals can also be replaced by an ether oxygen atom. Examples of aryl radicals are phenyl and naphthyl radicals, in which two phenyl groups can also be linked to one another via an oxygen atom. Examples of aralkyl radicals are those having 7 to 20 carbon atoms produced by combining a phenyl radical with an alkyl radical. Examples of heteroaryl radicals are pyridyl, pyrimidyl and furyl radicals. These radicals may also be further substituted, for example by alkyl, alkoxy, halogen, such as fluorine, chlorine or bromine, cyano, nitro, epoxy, carbonyl, ester groups, amides, etc. It is also possible for two of the radicals Ra, together with the atom M, to form a 3- to 6-membered ring, for example by two radicals Ra forming an alkylene chain, in which one or more CH2 groups may also be replaced by ether oxygen atoms.
If M is a transition metal, Ra can also be a conventional "sgr"- or xcfx80-bonded complex ligand, such as ethylene, allyl, butadiene, cyclopentadiene, mono- or polysubstituted cyclopentadienes, such as methylcyclopentadiene or pentamethylcyclopentadiene, benzene, cyclohexadiene, cycloheptatriene, cycloheptadiene, cyclooctatetraene, cyclooctatriene, cyclooctadiene, carbonyl, oxalato, cyano, isonitrile, fulminato-C, fulminato-O, cyanato, dinitrogen, ethyelenediamine, diethylenetriamine, triethylenetetramine, ethylenediamine tetraacetate, nitrosyl, nitro, isocyano, pyridine, xcex1,xcex1-dipyridyl, trifluorophosphine, phosphine, diphosphine, arsine or acetylacetonato.
Rb is particularly preferably hydrogen or methyl. Rc is hydrogen, C1-C4-alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl or butylisomers, phenyl, chlorine or an unsaturated hydrocarbon radical having 2 to 6 carbon atoms, such as vinyl, allyl, methallyl, butenyl or pentenyl.
Particularly suitable vinylaromatic compounds are those of the formula II 
where
R1 is hydrogen or C1- to C4-alkyl,
R2 to R6, independently of one another, are hydrogen, C1- to C12-alkyl, C6- to C18-aryl, or halogen, or two adjacent radicals together are a cyclic group having 4 to 15 carbon atoms.
Preference is given to vinylaromatic compounds of the formula II where
R1 is hydrogen, and
R2 to R6 are hydrogen, C1- to C4-alkyl, chlorine or phenyl, or two adjacent radicals together are a cyclic group having 4 to 12 carbon atoms, so that compounds of the formula II are, for example, naphthalene derivatives or anthracene derivatives.
Examples of preferred compounds of this type are the following:
styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene, 4-vinylbiphenyl, 2-vinylnaphthalene and 9-vinylanthracene.
It is also possible to use mixtures of different vinylaromatic compounds, where one component may also carry further hydrocarbon radicals, such as vinyl groups, allyl groups, methallyl groups, butenyl groups or pentenyl groups, preferably vinyl groups, on the phenyl ring. However, it is preferred to use only one vinylaromatic compound.
Particularly preferred vinylaromatic compounds are styrene and p-methylstyrene.
The preparation of vinylaromatic compounds of the formula II is known per se and is described, for example, in Beilstein 5, 367, 474, and 485.
The catalyst component A) used in accordance with the invention is a transition-metal complex from sub-group II to VIII, preferably from sub-group III to VIII. very particular preference is given to complexes of the metals titanium, zirconium and hafnium.
If the branching monomer unit of the formula I already contains a transition metal M, in particular titanium, it can, depending on the concentration used, also be used simultaneously as catalyst component A in addition to its function as branching unit.
The catalyst component A) is preferably a metallocene complex, particularly preferably of the formula III 
where
R7 to R11 are hydrogen, C1- to C10-alkyl, 5- to 7-membered cycloalkyl, which may itself carry C1- to C6-alkyl groups as substituents, C6- to C15-aryl or arylalkyl, it also being possible for two adjacent radicals together to form a cyclic group having 4 to 15 carbon atoms, or Si(R12)3, where
R12 is C1- to C10-alkyl, C6- to C15-aryl or C3- to C10-cycloalkyl,
M is a metal from sub-group III to VI of the Periodic Table of the Elements or a metal from the lanthanide series,
Z1 to Z5 are hydrogen, halogen, C1- to C10-alkyl, C6- to C15-aryl, C1- to C10-alkoxy or C1- to C15-aryloxy, and
z1 to z5 are 0, 1, 2, 3, 4 or 5, where the sum z1+z2+z3+z4+z5 corresponds to the valence of M minus 1.
Particularly preferred metallocene complexes of the formula III are those in which
M is a metal from sub-group IV of the Periodic Table of the Elements, ie. titanium, zirconium or hafnium, in particular titanium, and
Z1 to Z5 are C1- to C10-alkyl, C1- to C10-alkoxy or halogen.
Examples of preferred metallocene complexes of this type are the following:
Pentamethylcyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltrimethyltitanium and pentamethylcyclopentadienyltrimethoxytitanium.
It is also possible to use metallocene complexes as described in EP-A 584 646.
Mixtures of different metallocene complexes can also be used.
These complex compounds can be synthesized by methods known per se, preference being given to reaction of the appropriately substituted cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum.
Examples of appropriate preparation processes are described, inter alia, in Journal of Organometallic Chemistry, 369 (1989), 359-370.
Suitable metallocenium ion-forming compounds B) in the catalyst system are open-chain or cyclic aluminoxane compounds, for example of the formula IV or V 
where R13 is C1- to C4-alkyl, preferably methyl or ethyl, and k is an integer from 5 to 30, preferably from 10 to 25.
These oligomeric aluminoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water, as described, inter alia, in EP-A 284 708 and U.S. Pat. No. 4,794,096.
In general, the oligomeric aluminoxane compounds are obtained as a mixture of both linear and cyclic chain molecules of various lengths, so that k can be regarded as a mean value. The aluminoxane compounds can also be in the form of a mixture with other alkyl metal compounds, preferably alkylaluminum compounds.
It has proven advantageous to use the metallocene complexes and the oligomeric aluminoxane compounds in such amounts that the atomic ratio between aluminum from the oligomeric aluminoxane compound and the transition metal from the metallocene complex is in the range from 10:1 to 106:1, in particular in the range from 10:1 to 104:1.
The metallocenium ion forming compound B) can also be a coordination complex compound taken from the group consisting of strong, neutral Lewis acids, ionic compounds with Lewis-acid cations and ionic compounds with Bronsted acids as cations.
The strong, neutral Lewis acids are preferably compounds of the formula VI
MlX1X2X3xe2x80x83xe2x80x83(VI)
where
M1 is an element from main group III of the Periodic Table, in particular B, Al or Ga, preferably B,
X1, X2 and X3 are hydrogen, C1- to C10-alkyl, C6- to C15-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, or fluorine, chlorine, bromine or iodine, in particular haloaryls, preferably pentafluorophenyl.
Particular preference is given to compounds of the formula VI, in which X1, X2 and X3 are identical, preferably tris(pentafluorophenyl)borane. These compounds and processes for their preparation are known per se and are described, for example, in WO 93/3067.
Suitable ionic compounds with Lewis-acid cations are compounds of the formula VII
xe2x80x83[(Ya+)Q1Q2. . . Qz]d+xe2x80x83xe2x80x83(VII)
where
Y is an element from main group I to VI or sub-group I to VIII of the Periodic Table,
Q1 to Qz are radicals with a single negative charge, such as C1- to C28-alkyl, C6- to C15-aryl, alkylaryl, arylalkyl, haloalkyl, and haloaryl, each having 6 to 20 carbon atoms in the aryl radical and 1 to 28 carbon atoms in the alkyl radical, C1- to C10-cycloalkyl, which is unsubstituted or substituted by C1- to C10-alkyl, or are halogen, C1- to C28-alkoxy, C6- to C15-aryloxy, silyl- or mercaptyl groups,
a is an integer from 1 to 6,
z is an integer from 0 to 5, and
d is the difference axe2x88x92z, but where d is greater than or equal to 1.
Particularly suitable are carbonium cations, oxonium cations, sulfonium cations and cationic transition-metal complexes. Particular mention should be made of the triphenylmethyl cation, the silver cation and the 1,1xe2x80x2-dimethylferrocenyl cation.
They preferably have non-coordinating counterions, in particular boron compounds, as also mentioned in the WO 91/09882, preferably tetrakis(pentafluorophenyl) borate.
Ionic compounds with Brxc3x6nsted acids as cations and preferably likewise non-coordinating counterions are mentioned in WO 93/3067; the preferred cation is N,N-dimethylanilinium.
It has proven particularly suitable if the molar ratio between boron from the metallocenium ion forming compound and transition metal from the metallocene complex is in the range from 0.1:1 to 10:1, in particular in the range from 1:1 to 5:1.
The catalyst system employed in the novel process can contain an aluminum compound as component C), for example of the formula VIII
AlR14R15R16xe2x80x83xe2x80x83(VIII),
where
R14 to R16 are hydrogen, fluorine, chlorine, bromine, iodine or C1- to C12-alkyl, preferably C1- to C8-alkyl.
The radicals R14 and R15 are preferably identical C1-C6-alkyl radicals, such as methyl, ethyl, isobutyl or n-hexyl; R16 is preferably hydrogen.
Component C) is preferably present in the catalyst system in an amount from 1:2000 to 1:1, in particular from 1:800 to 1:10 (molar ratio between transition metal from III and Al from VIII).
The solvent used for the metallocene complex is usually an aromatic hydrocarbon, preferably having 6 to 20 carbon atoms, in particular xylene, toluene, ethylbenzene, or a mixture thereof.
The metallocene complexes may if desired be supported.
Examples of suitable support materials are silica gels, preferably those of the formula SiO2.bAl2O3, in which b is a number in the range from 0 to 2, preferably from 0 to 0.5; ie. essentially aluminosilicates or silicon dioxide. The supports preferably have a particle diameter in the range from 1 to 200 xcexcm, in particular from 30 to 80 xcexcm. Such products are commercially available, for example as Silica Gel 332 from Grace.
Other supports include finely divided polyolefins, for example finely divided polypropylene or polyethylene, but also polyethylene glycol, polybutylene terephthalate, polyethylene terephthalate, polyvinyl alcohol, polystyrene, syndiotactic polystyrene, polybutadiene, polycarbonates or copolymers thereof.
The molar ratio between transition-metal catalyst A) and vinylaromatic monomer is generally from 1:1000 to 1:10,000,000, but preferably from 1:2000 to 1:1,000,000.
The present invention furthermore provides a process for the preparation of novel star polymers which can be carried out by observing the process conditions mentioned. A particular embodiment of the process comprises using a co-rotating, tightly meshing and thus self-cleaning twin-screw extruder, preferably in one step.
The reaction temperature is generally from xe2x88x9280 to 150xc2x0 C., preferably from 0 to 120xc2x0 C. However, it is also possible to apply a temperature gradient from 0 to 120xc2x0 C. to the reaction tube via heatable jackets.
The extruder can consist of a plurality of individual zones which can be held at different temperatures.
The outer diameter of the corotating, preferably double-flighted compounding and conveying elements of the twin-screw extruder is preferably in the range from 25 to 70 mm, in particular from 30 to 58 mm.
The free space between the extruder barrel and the screw element is in the range from 0.2 to 0.8 mm, in particular from 0.3 to 0.5 mm.
The screw speed can be in the range from 3 to 500 revolutions per minute, preferably from 5 to 30 revolutions per minute.
The mean residence time in the extruder can be from 0.1 to 240 minutes, preferably from 2 to 20 minutes.
The mean residence time in the extruder can be regulated via the number of barrel blocks, which is preferably in the range from 6 to 20, in particular from 8 to 12, but particularly preferably 10, backventing taking place in the first block, the starting materials being metered into the second block, the reaction taking place in blocks 3 to 8, blocks 9 and 10 being heated to different temperatures if desired, and discharge taking place in block 10.
The process is preferably carried out in such a way that the vinylaromatic compound, the branching monomer unit, the metallocenium ion-forming compound B) and, if used, the aluminum compound C) are mixed under an inert-gas atmosphere and fed to the first extruder barrel block. In parallel, a solution or suspension of the transition-metal complex (A) can likewise be fed to the first block (zone).
Solvents and suspending media which may be mentioned are cyclic and acyclic hydrocarbons, such as butanes, pentanes, hexanes and heptanes, furthermore aromatic hydrocarbons, such as benzene, toluene and ethylbenzene, and oxygen-containing hydrocarbons, such as tetrahydrofuran, halogen-containing hydrocarbons, such as dichloromethane, and nitrogen-containing hydrocarbons, such as N-methylpiperidine, and mixtures thereof.
The amount metered in is preferably selected so that from 500 to 2000 g/h of the mixture of vinylaromatic compound, component B) and, if used, component C) are fed in along with from 100 to 200 cm3/h of the solution or suspension of the metal complex.
The polymerization is preferably carried out in the vinylaromatic compound as reaction medium, ie. in bulk.
The process is technically simple to carry out, high conversions are achieved, and the risk of sticking or blockage of the extruder outlet apertures is low.
A further preferred embodiment comprises activating the reaction mixture of the vinylaromatic monomers, the branching monomer unit and the catalyst system consisting of A) a transition-metal complex from sub-group II to VIII, B) a cation-forming agent and C), if desired, an aluminum compound, by premixing and subsequently polymerizing the mixture in a mixer/compounder.
The premixing is preferably carried out at a temperature at which the reaction mixture is still liquid and the polymerization does not commence. Depending on the components used for the reaction mixture, this temperature is in the range from xe2x88x9230 to +140xc2x0 C., preferably from 0 to 70xc2x0 C., particularly preferably from 15 to 30xc2x0 C. Furthermore, in the case of the novel activation, the premixing should preferably be carried out in such a way that the residence time and temperature are selected so that there is no damage to the catalyst, in spite of mixing sufficient for activation, and the polymerization reaction does not commence.
The activation by premixing the reaction mixture is advantageously carried out shortly or immediately before the polymerization reaction. The time between activation by premixing and polymerization is from 0 to 60 minutes, especially from 0.01 to 45 minutes, and particularly preferably from 0.1 to 30 minutes, it being preferred for the premixing to be carried out essentially without a reaction commencing.
The process is advantageously carried out without a solvent. In a particularly preferred embodiment of the process, the monomers employed initially act as solvent. In addition, it is advantageous to carry out the process in an inert-gas atmosphere, for example comprising nitrogen or argon, if possible with exclusion of moisture. It is also possible to meter hydrogen into the inert-gas stream.
The premixing is preferably carried out in such a way that no reaction takes place. It is furthermore advantageous that polymers are obtained in such a way that they can be processed further, preferably extruded, essentially immediately after the polymerization. This is preferably the case if the polymerization process is carried out to high yields and the polymer accordingly has a low residual monomer content of below 10% by weight, preferably below 5% by weight, particularly preferably below 3% by weight, based on the weight of the polymer. The residual monomer content remaining in the polymer can be removed, for example, by evaporation or by applying a vacuum. The novel process is preferably carried out in a mixing/compounding reactor with a downstream extruder without further work-up steps, for example removal of relatively large amounts of monomer, which are produced, in particular, at low conversions, by distillation, being necessary. The process thus permits further processing of the polymer essentially immediately after its preparation.
The resultant star polymers having syndiotactic chain branches and high molecular weights in combination with low melt viscosity are suitable for the production of fibers, for example monofilaments, films and moldings, in particular injection molding materials [sic] for electrical or high-temperature-resistant applications. Owing to their high olefinic end group content, they can also be modified by grafting, crosslinking or other polymer-analogous reactions and can be processed alone or in blends with thermoplastic polymers, rubbers, fillers, etc.